JP2749663B2 - Mixtures of polycarbonate with other thermoplastics or elastomers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides: a) the following formula (I): Wherein R ¹ and R ² independently of one another are hydrogen, halogen, C ₁ -C ₈ -alkyl, C ₅ -C ₆ -cycloalkyl, C ₆ -C ₁₀ -aryl, and C ₇ -C ₁₂ -aralkyl Where m is an integer from 4 to 7, and at least one atom X, wherein both R ³ and R ⁴ both represent alkyl, R ³ and R ⁴ are individually X may be selected independently of _{one another} and represent hydrogen or C ₁ -C ₆ -alkyl, X represents a hydrocarbon, and b) a thermoplastic polycarbonate based on diphenol, and b) other than the estramers or components a) The present invention relates to thermoplastics and optionally c) mixtures comprising standard additives, their preparation, and their use for the production of films.

German Patent Application P3 832 396.6 describes the polycarbonates (a) of the mixtures according to the invention and their raw materials and their preparation.

The starting product of the polycarbonate (a) has the formula (I) Wherein R ¹ and R ² independently of one another are hydrogen, halogen, preferably chlorine or bromine, C ₁ -C ₈ -alkyl, C ₅ -C ₆ -cycloalkyl, C ₆ -C ₁₀ aryl, preferably phenyl , And C ₇
-C ₁₂ - aralkyl, preferably phenyl -C ₁ -C ₄ -
M represents an integer from 4 to 7, preferably 4 or 5;
And, assuming to represent both alkyl both R ³ and R ⁴ on at least one atom X, well R ³ and R ⁴ are selected for each X individually, hydrogen independently of each other or C ₁ -C ₆ - alkyl, X is dihydroxydiphenyl cycloalkanes corresponding to represents a carbon atom.

Preferably, R ³ and R ⁴ are simultaneously one or two atoms X
Represents an alkyl, especially on a single atom X. The preferred alkyl group is methyl; the X atom in the α-position to the diphenyl-substituted carbon atom (C-1) is preferably not dialkyl-substituted, in contrast to the β-position to C-1. Dialkyl substitution at the position is preferred. X atom at the β-position to C-1 is dialkyl-substituted, and β ′
Most preferably, the X atom in the -position is -alkyl substituted.

Preferred dihydroxydiphenylcycloalkanes are
A cycloaliphatic radical having 5 to 6 ring carbon atoms [wherein m represents 4 or 5 in formula (I)], for example: as well as And 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula II) is particularly preferred.

The dihydroxydiphenylcycloalkane (I) corresponding to formula (I) is a phenol corresponding to formula (V): And the ketone corresponding to formula (VI): In the formulas (V) and (VI), X, R ¹ , R ² , R ³ , R ⁴ and m are the same as defined in the formula (I). Can be.

The phenol corresponding to the formula (V) is a substance known from the literature or a substance obtained by a method known from the literature (for cresol and xylenol, for example, Ullmann, Enzyklopadi
e der technishen Chemie), 4th revised supplement, 15th edition
Vol. 61-77, Veralag Chemi
e), Weinheim / New York, 1978;
Regarding chlorophenols, Ullman, Encyclopedia of Industrial Chemistry,
4th edition, Verlag Hemy, 1979, Volume 18, 191-21
See page 4.)

Examples of suitable phenols corresponding to formula (V) are phenol, o-cresol, m-cresol, 2,6-dimethylphenol, 2-chlorophenol, 3-chlorophenol, 2,6-dichlorophenol, 2-cyclohexyl Phenol, 2,6-diphenylphenol, and o-benzylphenol.

The ketones corresponding to the formula (IV) are substances known from the literature (see, for example, the following literature): Beilstein, Handbook of Organic Chemistry (Beilsteis Handbuch der o)
rganischen Chemie), Volume 7, Fourth Edition, Springer-Verlag, Berlin, 192
5, and the corresponding addendum, Volumes 1-4, and the Journal of American Chemical Society (J.
Am. Chem. Soc.) 79, (1957), pp. 1488-1492, U.S. Pat. No. 2,692,289, Journal of Chemical Society (J. Chem. Soc.) (1959), pp. 2186-2192, and Journal・ Organic Chemistry (J.Org.)
Chem.) 38, (1973), p. 4431-4435, Journal of American Chemical Society 87 , (1965)
General methods for the preparation of ketones corresponding to formula (VI) are described, for example, in "Organik
m) ", 15th edition, 1977, VEB-Deutcher Science Publishing (VEB
-Deutscher Verlag der Wissenschaften Berlin), Berlin, eg, page 698.

Examples of known ketones corresponding to formula (VI) are: 3,3-dimethylcyclopentanone, 2,2-dimethylcyclohexanone, 3,3-dimethylcyclohexanone, 4,4-dimethylcyclohexanone, 3-ethyl-3- Methylcyclopentanone, 2,3,3-trimethylcyclopentanone, 3,3,4-trimethylcyclopentanone, 3,3-dimethylcycloheptanone, 4,4-dimethylcycloheptanone, 3-ethyl-3 -Methylcyclohexanone, 2,4,4-trimethylcyclohexanone, 3,34-trimethylcyclohexanone,
3,3,5-trimethylcyclohexanone, 3,4,4-trimethylcyclohexanone, 3,3,5-trimethylcycloheptanone, 3,5,5-trimethylcycloheptanone, 5-ethyl-2,5-dimethylcyclo Heptanone, 2,3,3,5-tetramethylcycloheptanone, 2,3,5,5-tetramethylcycloheptanone, 3,3,5,5-tetramethylcycloheptanone, 4-ethyl-2 , 3,4-Trimethylcyclopentanone, 3-ethyl-4-isopropyl-3-methylcyclopentanone, 4-tert-butyl-3,3-dimethylcyclopentanone, 2-isopropyl-3,3,4- Trimethylcyclopentanone, 3-ethyl-4-isopropyl3-3methylcyclohexanone, 4-ethyl-3-isopropyl-4-methylcyclohexanone, 3-tert-butyl-4,4
-Dimethylcyclohexanone, 2-butyl-3,3,4-trimethylcyclopentanone, 2-butyl-3,3,4-trimethylcyclohexanone, 4-butyl-3,3,5-trimethylcyclohexanone, 3-isohexyl-3 -Methylcyclohexanone and 3,3,8-trimethylcyclooctanone.

Examples of preferred ketones are: and It is.

To produce the above bisphenols, generally 2 to 10 mol, preferably 2.10 mol per mol of ketone (IV).
5 to 6 moles of phenol (V) are used. The preferred reaction time is 1 to 100 hours. The reaction is generally carried out between -30 and 300 ° C, preferably between -15 and 150 ° C.
At a temperature of 1 to 20 bar, preferably 1 to 10 bar
It is carried out under a pressure of

The above condensation is generally carried out in the presence of an acid catalyst. Examples are hydrogen chloride, hydrogen bromide, hydrogen fluoride, boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, phosphorus halide, phosphorus pentoxide, phosphoric acid, concentrated hydrochloric acid or concentrated sulfuric acid, And a mixture of acetic acid and acetic anhydride. It is also possible to use acidic ion exchangers.

The above reaction further comprises a co-catalyst, such as a C ₁ -C ₁₈ -alkyl mercaptan, hydrogen sulfide, thiophenol, thioacid and dialkyl sulfide, preferably at a concentration of 0.1 mole per mole of ketone.
01 to 0.4 mol, especially 0.05 to 0.4 mol per mol of ketone
Acceleration can be achieved by adding 0.2 moles.

The above condensation can be carried out without solvent or in the presence of inert solvents (for example aliphatic and aromatic hydrocarbons or chlorohydrocarbons).

It is not necessary to use a separate dehydrating agent if the catalyst also functions as a dehydrating agent at the same time, but if the used catalyst does not combine with the water generated in the reaction, it is necessary to use a dehydrating agent to achieve good conversion. Use is advantageous.

Examples of suitable dehydrating agents are, for example, acetic anhydride, zeolites, polyphosphoric acid and phosphorus pentoxide.

Phenol (V) and ketone (VI) are (V) versus (VI)
Is 2: 1 to 10: 1, and preferably 2.5: 1 to 6:
1, at -30 ° C to 300 ° C, preferably -15 ° C to 150 ° C
At a temperature of 1 to 20 bar, and preferably 1 to 10 ba
Under a pressure of r, it is possible to react in the presence of an acidic catalyst and optionally in the presence of a cocatalyst and / or a solvent and / or a dehydrating agent.

In formula (I), R ³ and R ⁴ are preferably both alkyl at the same time on one or two atoms X, but are particularly preferably alkyl on only one atom X. A preferred alkyl group is methyl,
Ethyl or linear or branched C ₃ -C ₆ alkyl groups may be used. The X atom that is α-position to the diphenol-substituted C atom (C-1) is preferably not dialkyl-substituted, but the X atom that is β-position to C-1 is dialkyl-substituted. Is preferred. Compounds in which one β-position is dialkyl substituted and the other β-position is mono-alkyl substituted are most preferred.

In many cases, the response is not completely uniform,
That is, several different products can result, and the desired product must first be isolated from the mixture. See Schnell, Chemistry and Physics for polycarbonates for details of the reaction.
of Polycarbonates, Interscience Publishers, New York, 1964. In some cases, it is possible to control the reaction in such a way as to precipitate or crystallize the compound to make isolation of the desired compound easier through appropriate catalysts and reaction conditions. The preparation of the diphenol corresponding to formula (II) is described below.

Example A.1 7.5 mol (705 g) in one round bottom flask equipped with stirrer, dropping funnel, thermometer, reflux condenser and gas inlet tube.
Of phenol and 0.15 mol (30.3 g) of dodecylthiol and saturate dry HCI gas at 28-30 ° C. 1.5 mol (210 g) of dihydroisophorone (3,3,5-trimethylcyclohexane-1-one) was added to the resulting solution.
And 1.5 mol (151 g) of phenol are added dropwise over 3 hours. At this time, the HCI gas is kept flowing through the reaction solution. After the addition, HCI gas is introduced for a further 5 hours. The mixture is then reacted at room temperature for 8 hours. The excess phenol is then removed by steam distillation. The residue is extracted twice with hot petroleum ether (60-90) and once with methylene chloride and filtered off. Yield: 370 g. Melting point: 205-207 ° C.

Example A.2 Preparation of diphenol of formula (II) In a stirrer equipped with a stirrer, thermometer, reflux condenser and gas inlet tube, 1692 g (18 mol) of phenol, 60.6 g
(0.3 mol) of dodecylthiol and 420 g (3 mol) of dihydroisophorone (3,3,5-trimethylcyclohexane-1-one) are introduced at 23-30.degree. Dry H in this solution
CI gas is introduced at 28-30 ° C. over 5 hours. The mixture is then reacted at 28-30 ° C. for about 10 hours. When 95% of the ketone has been converted (tested by GC), 2.5 l of reaction mixture
Of water and the pH is adjusted to 6 by adding 45% NaOH.
The reaction mixture is stirred at 80 ° C for 1 hour and then cooled to 25 ° C. Discard the aqueous phase by decantation and remove the remaining residue by 80.
Wash with water at ° C. The resulting crude product is filtered off and n-
Extract twice with hexane and twice with methylene chloride, then filter. The residue is recrystallized twice from xylene.

Yield: 753 g Melting point: 209-211 ° C. Example A.3 Preparation of diphenol of formula (II) 564 g (6 mol) in a stirrer equipped with a stirrer, thermometer, reflux condenser and gas inlet tube. Phenol, 10.8g
(0.12 mol) of butanethiol and 140 g (1 mol) of dihydroisophorone (3,3,5-trimethylcyclohexane-1-one) are introduced at 30 ° C. At this temperature, 44 g of 37% HCl gas is added. The reaction mixture is then stirred at 28-30 ° C. for about 70 hours. When 95% of the ketone was converted (tested by GC), 2 l of water was added to the reaction mixture and 45% NaOH was added.
Adjust the pH value to 6. The reaction mixture is stirred at 80 ° C. for 1 hour and then cooled to 25 ° C. The aqueous phase is decanted off and the remaining residue is washed with water at 80 ° C. The crude product obtained is filtered off, hot-extracted twice with n-hexane and twice with methylene chloride and then filtered at 30 ° C.

Yield: 253 g Melting point: 205-208 ° C. Example A.4 Preparation of diphenol of formula (Ib) (R ¹ and R ² = CH ₃ ) Equipped with stirrer, thermometer, reflux condenser and gas inlet tube In a stirrer, 2196 g (18 mol) of 2,6-dimethylphenol, 38.2 g (0.36 mol) of β-mercaptopropionic acid and 420 g (3 mol) of dihydroisophorone (3,3,
5-trimethylcyclohexane-1-one) is introduced at 35 ° C. To this solution is introduced dry HCl gas at 35 ° C. over 5 hours. The mixture is then reacted at 28-30 ° C. for about 10 hours. When 95% of the ketone is converted (tested by GC), 2.5 l of water are added to the reaction mixture and the pH is adjusted to 6 by adding a 45% NaOH solution. Bring the reaction mixture to 80 ° C for 1
Stir for hours and then cool to room temperature. The aqueous phase is decanted off and the remaining residue is washed with water at 60 ° C. The crude product obtained is filtered off, hot extracted three times with n-hexane and then filtered.

Yield: 856 g Melting point: 236-238 ° C. Example A.5 Preparation of a diphenol of the formula (III) By the same method as in Example A.2, instead of 3 mol of dihydroisophorone, 3 mol of 3,3-dimethyl Use cyclohexane. The melting point of the product was 199-201 ° C.

Polycarbonates can be prepared from the diphenols corresponding to formula (I) according to German Patent Application P 38 32 396.6.

It is possible to use both a single diphenol corresponding to formula (I) and several diphenols corresponding to formula (I), in the former case a homopolycarbonate is formed, in the latter case Produces a copolymerized polycarbonate.

Furthermore, diphenols corresponding to magnetism (I) are also used to produce high molecular weight thermoplastic aromatic polycarbonates,
It can be used in a mixture with other diphenols, for example those corresponding to the formula HO-Z-OH (VIII).

Other suitable diphenols corresponding to the formula HO-Z-OH (VIII) are those wherein Z may contain one or more aromatic nuclei, may be substituted, and aliphatic residues or Diphenols which are aromatic residues containing from 6 to 30 carbon atoms, which may contain heteroatoms as cycloaliphatic residues or bridging components other than those corresponding to formula (I).

Examples of diphenols corresponding to formula (VII) are hydroquinone, dihydroxydiphenyl, bis- (hydroxyphenyl) -alkane, bis- (hydroxyphenyl)-
Cycloalkane, bis- (hydroxyphenyl) -sulfide, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfone, bis- (hydroxyphenyl) -sulfoxide, α, α'-bis- (hydroxyphenyl) -diisopropylbenzene and their halogenated compounds.

These and other suitable diphenols are described, for example, in U.S. Patent Nos. 3,028,365, 2,999,835, 3,148,172, 3,275,601.
No. 2,991,273, 3,271,367, 3,062,781, 2,970,1
Nos. 31 and 2,999,846; German Patent Publication No. 1,570,7
No. 03, 2,063,050, 2,063,052, 2,221,0956; French Patent No. 1,561,518, and H. Schnell, entitled "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York, 1964, supra. Schnell).

Other suitable diphenols are, for example, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, α, α′-bis (4
-Hydroxyphenyl) -p -diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3-chloro-4-hydroxyphenyl) propane, bis- ( 3,5-dimethyl-
4-hydroxyphenyl) -methane, 2,2-bis- (3,5
-Dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane,
α, α'-bis- (3,5-dimethyl-4-hydroxyphenyl) -p -diisopropylbenzene, 2,2-bis-
(3,5-dichloro-4-hydroxyphenyl) -propane and 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane.

Particularly suitable diphenols corresponding to formula (VII) are, for example, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane , 2,2-bis- (3,5-dichloro-4-
(Hydroxyphenyl) -propane, 2,2-bis- (3,5-
Dibromo-4-hydroxyphenyl) -propane and 1,
1-bis- (4-hydroxyphenyl) -cyclohexane.

2,2-bis- (4-hydroxyphenyl) -propane is particularly preferred.

Other diphenols may be used individually and mixed with one another.

A diphenol corresponding to formula (I) vs. optionally used,
For example, the molar ratio of other diphenols corresponding to formula (VIII) may range from 100 mole% of (I) to 0 mole% of other diphenols to 2 mole% of (I) to 98 mole% of other diphenols, preferably (I) 100 mol% to 0 mol% of other diphenols to 5 mol% of (I) to 95 mol% of other diphenols, and more preferably (I) 100 mol% to 0 mol% of other diphenols.
Or (I) 10 mole% to 90 mole% of other diphenols, and most preferably (I) 100 mole% to 0 of other diphenols.
Mol% to (I) 20 mol% to other diphenols 80 mol%.

The high molecular weight polycarbonate of the diphenol corresponding to formula (I), optionally in combination with other diphenols, can be made by any of the known methods used to make polycarbonates.

At that time, various diphenols can be bonded to each other to form random and block copolymers.

The polycarbonate may be branched in a known manner. If branching is required, a small amount, preferably 0.05 to
By co-condensing 2.0 mol% (relative to the diphenol used) of a trifunctional or trifunctional or higher compound, in particular a compound containing three or more phenolic hydroxyl groups, in a known manner Can be achieved. Branching agents containing three or more phenolic hydroxyl groups are phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept-2-ene,
4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4 -Hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl)
-Phenylmethane, 2,2-bis- (4,4-bis- (4-hydroxyphenyl) -cyclohexyl) -propane,
4-bis- (4-hydroxyphenylisopropyl)-
Phenol, 2,6-bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenol) -2- (2,4-dihydroxyphenyl) propane, hexa- (4 -(4-hydroxyphenyl-isopropyl) -phenyl) -ortho-terephthalic acid ester, tetra- (4-hydroxyphenyl)-
Methane, tetra- (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane and 1,4-bis-
((4 '-, 4 "-dihydroxytriphenyl) -methyl) -benzene.

Examples of other trifunctional compounds include 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3
-Bis- (3-methyl-4-hydroxyphenyl) -2
-Oxo-2,3-dihydroindole.

Monofunctional compounds can be used in known concentrations at known concentrations as chain stoppers for controlling the molecular weight of the polycarbonate (a). Suitable compounds are, for example, phenol, tert.-butylphenol or other alkyl-C
₁ -C ₇ - substituted phenol. Formula (VIII) In the above formula R is a C ₈ and / or alkyl groups branched, a small amount of phenol corresponding to is particularly suitable for regulating molecular weight. In the alkyl residue R, the percentage of CH ₃ protons is 4
7 to 89%, the percentage of protons of CH and CH ₂ is 53 to 11
%. R is preferably in the o- and / or p-position to the OH group, and a particularly preferred upper limit of the ortho component is 20%. Chain terminators are generally used in an amount of 0.5 mol to 10 mol%, and preferably in an amount of 1.5 to 8 mol%, based on the diphenol used.

Polycarbonate (a) is prepared in a known manner, preferably by the method of interfacial polycondensation (H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer, Reviews).
s), Volume IX, p. 33 or less, see Interscience Publ, 1964). In this method, the formula (I)
Is dissolved in the aqueous alkaline phase.
For the production of copolymerized polycarbonates with other diphenols, a mixture of a diphenol corresponding to formula (I) and another diphenol, for example a diphenol corresponding to formula (VIII), is used. To adjust the molecular weight, for example, a chain terminator corresponding to formula (VIII) can be added. The reaction is then carried out using phosgene by a phase interface polycondensation process in the presence of an inert, preferably polycarbonate-soluble organic phase. Reaction temperature is 0 to 40 ° C
Range.

The optional branching agent (preferably 0.05 to 2 mol%) may be initially introduced with the diphenol into the aqueous alkaline phase or may be added to the solution in the organic solvent before phosgenation. .

In addition to the diphenols of the formula (I), it is also possible, if desired, to use other diphenols (VIII), their mono- and / or bis-chloroformates, in which case they are dissolved in organic solvents and added. You. The amount of chain terminator and branching agent used is determined by the molar amount of diphenolate residue corresponding to formula (I) and optionally formula (VII). If chloroformates are used, the amount of phosgene can be reduced in a known manner.

Suitable solvents for the chain terminator and, if appropriate, the branching agent and the chloroformate are, for example, methylene chloride, chlorobenzene, acetone, acetonitrile and mixtures of these solvents, in particular a mixture of methylene chloride and chlorobenzene. The chain stoppers and branching agents used may optionally be dissolved in the same solvent.

As the organic solvent for the phase interface polycondensation, for example, methylene chloride, chlorobenzene, and a mixture of methylene chloride and chlorobenzene are used.

As the aqueous alkaline phase, for example, an aqueous solution of HaOH is used.

The preparation of the polycarbonates (a) by the phase interface polycondensation process is contacted in a conventional manner with a catalyst such as a tertiary amine, in particular a tertiary aliphatic amine, for example tributylamine or triethylamine. The catalyst is used in an amount of 0.05 to 10 mol%, based on the moles of diphenol used. The catalyst may be added before or during or after phosgenation.

Polycarbonates (a) can also be prepared by known homogeneous phase processes, the so-called "pyridine process" and also by known melt transesterification processes, for example, using diphenyl carbonate instead of phosgene.

The molecular weight _w of the polycarbonate (a) (weight average molecular weight, determined by gel chromatography after shading in advance) is at least 10,000, and more preferably 10,000.
Most preferably, it is in the range of 00 to 300,000, and in the range of 20,000 to 80,000 when polycarbonate is used in the manufacture of injection molded articles. They may be straight-chain or branched. And the polycarbonate (a) is a homogeneous or copolycarbonate based on diphenyl corresponding to the formula (I).

Thus, polycarbonates (a) within the meaning of the invention have a molecular weight of at least 10,000, and preferably in the range of 10,000 to 300,000, and more preferably 20,000 to 8 if polycarbonate is used for the production of injection molded articles.
It has a _w value (weight average molecular weight) in the range of 0,000 and has the formula (1a) Wherein X, R ¹ , R ² , R ³ , R ⁴ and m are as defined in formula (I), wherein a bifunctional carbonate structural unit corresponding to 100 mol% to 2 mol%, based on the total amount of the structural units of the basic carbonate as 100 mol%
Preferably in an amount of 100 mol% to 5 mol%, more preferably in an amount of 100 mol% to 10 mol%, and most preferably in an amount of 100 mol% to 20 mol%. High molecular weight, thermoplastic, aromatic polycarbonate.

The polycarbonates are thus each present in amounts up to 100 mol% in each case, for example of the formula (VIIa) In formula (VIIa), -Z- corresponds to -Z- in formula (VII), and in each case the total amount of difunctional carbonate structural units in the polycarbonate With respect to 100 mol%, from 0 mol% (inclusive) to 98 mol% (inclusive), preferably 0 mol% to 95 mol%, more preferably 0 mol% to 90 mol%, and Most preferably it is present in an amount of 0 mol% to 80 mol%.

New polycarbonates having high heat resistance along with other advantageous properties are obtained by incorporation of diphenols corresponding to formula (I). This is especially where m is 4 or 5,
In polycarbonates based on diphenols (I), in particular the compounds of the formula (Ib) Wherein R ¹ and R ^2, which are mutually independent, have the meaning defined in formula (I) and more preferably represent hydrogen, and are applied in a diphenol-based polycarbonate corresponding to

Suitable polycarbonates (a) are polycarbonates in which m is 4 or 5 in the structural unit corresponding to formula (Ia), in particular formula (Ic) Wherein R ¹ and R ² have the meaning defined in formula (Ia) but are preferably hydrogen, a unit of polycarbonate corresponding to:

These compounds of formula (Ib), wherein R ¹ and R ² are preferably hydrogen
Polycarbonates based on diphenols, in addition to their high heat resistance, also exhibit high UV stability and good flow behavior of the melt.

In addition, the properties of polycarbonate are other diphenols,
In particular, it can be advantageously varied by combination with a diphenol corresponding to formula (VII).

Examples B.1 to B.5 below are polycarbonate (a)
The production of is described. The relative viscosity was measured in 0.5 wt% solution of polycarbonate was dissolved in CH ₂ Cl _2.

Glass transition temperature was measured by differential scanning calorimetry (DSC).

Example B.1 31.0 g (0.1 mol) of diphenol of Example (A.1), 3
3.6 g (0.6 mol) of KOH and 560 g of water are dissolved with stirring in an inert gas atmosphere. Then a solution of 0.188 g of phenol in 560 ml of methylene chloride is added. pH
19.8 g (0.2 mol) of phosgene were introduced into the thoroughly stirred solution at 13 to 14 and at a temperature of 21 to 25 ° C., then 0.1 ml of ethylpyridine were added, followed by stirring for 45 minutes. The aqueous phase without bisphenol was separated off, acidified with phosphoric acid and the organic phase was washed with water until neutral,
The solvent was removed. The polycarbonate had a relative viscosity of 1.259.

The glass transition temperature of the polymer was found to be 233 ° C (DSC).

Example B.2 68.4 g (0.3 mol) of bisphenol A (2,2-bis-
(4-hydroxyphenyl) -propane), 217.0 g (0.
7 mol) of the diphenol of example (A.1), 336.6 g (6 mol) of KOH and 2700 g of water are dissolved in an inert gas atmosphere with stirring. Then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added. pH 13 or 14
And 198 g (2 mol) of phosgene were introduced into the solution, which was thoroughly stirred at a temperature between 21 and 25 ° C., then 1 ml of ethylpyridine were added, followed by stirring for 45 minutes. The aqueous phase free of bisphenol was separated off, acidified with phosphoric acid and the organic phase was washed with water until neutral and the solvent was removed. The polycarbonate had a relative viscosity of 1.336.

The glass transition temperature of the polymer was found to be 212 ° C (DSC).

Example B.3 A mixture of 114 g (0.5 mol) of bisphenol A and 155 g (0.5 mol) of the diphenol of example (A.1)
The reaction was carried out as in B.2 to form polycarbonate.

 The polycarbonate had a relative viscosity of 1.386.

The glass transition temperature of the polymer was found to be 195 ° C (DSC).

Example B.4 159.6 g (0.7 mol) of bisphenol A and 93 g (0.3
Mol) of the diphenol of Example (A.3) was reacted as in Example B.2 to form a polycarbonate.

 The polycarbonate had a relative viscosity of 1.437.

The glass transition temperature of the polymer was found to be 180 ° C (DSC).

Example B.3 31.0 g (0.1 mol) of diphenol of Example (A.3), 2
4.0 g (0.6 mol) of NaOH and 270 g of water are dissolved with stirring in an inert gas atmosphere. Then a solution of 0.309 g of 4- (1,1,3,3-tetramethylbutyl) -phenol in 250 ml of methylene chloride is added. pH 13 or 14
And 19.8 g (0.2 mol) of phosgene are introduced into a thoroughly stirred solution at a temperature of 21 to 25 ° C. and then 0.1 ml
Of ethyl pyridine was added and stirring was continued for 45 minutes. The aqueous phase free of bisphenol was separated off, acidified with phosphoric acid and the organic phase was washed with water until neutral and the solvent was removed. The polycarbonate had a relative viscosity of 1.314.

The glass transition temperature of the polymer was found to be 234 ° C (DSC).

Example B.6 148.2 g (0.65 mol) of 2,2-bis- (4-hydroxyphenyl) -propane, 108.5 g (0.35 mol) of diphenol of example (A.1), 336.6 g (6 mol) ) KOH, and
2700 g of water are dissolved with stirring in an inert gas atmosphere. Then 8.86 g of 4 dissolved in 2500 ml of methylene chloride
Add a solution of-(1,1,3,3-tetramethylbutyl) -phenol. 198 g (2 mol) of phosgene are introduced into a thoroughly stirred solution at pH 13-14 and at a temperature of 21-25 ° C. Then 1 ml of ethylpyridine is added and the mixture is subsequently stirred for 45 minutes. The aqueous phase free of bisphenolate was separated off, acidified with phosphoric acid and the organic phase was washed neutral with water to remove the solvent. Polycarbonate is 1.
It had a relative viscosity of 20.

Example B.7 3.875 kg (12.5 mol) of the bisphenol of example (A.2) are dissolved with stirring in 6.675 kg of 45% NaOH and 30 l of water in an inert gas atmosphere. Then 9.43 l of methylene chloride, 11.3 l of chlorobenzene and 23.5 g of phenol are added. 2.475 kg of phosgene are introduced into the well-stirred solution at pH 13-14 and at a temperature of 20-25 ° C. After the introduction is complete, 12.5 ml of N-ethylpyridine are added. The mixture is then reacted for 45 minutes. The aqueous phase free of bisphenolate is separated off, the organic phase is acidified with phosphoric acid, washed until the electrolyte is gone, and the solvent is removed.

Relative viscosity: 1.300 Glass transition temperature: 238 ° C.

Example B.8 15.5 g (0.05 mol) of the bisphenol of Example A.3, 1
3.4 g (0.05 mol) of bis- (4-hydroxyphenyl)
-Cyclohexane (bisphenol Z) and 24.0 g (0.6
Mol) of NaOH with stirring in an inert gas atmosphere.
Dissolve in l of water. Then 0.516 g of 4- (1,1,3,3-tetramethylbutyl) dissolved in 271 ml of methylene chloride
Add phenol. 19.8 g of phosgene are introduced into a thoroughly stirred solution at pH 13-14 and at a temperature of 20-25 ° C. Five minutes after the introduction is complete, 0.1 ml of N-ethylpyridine is added. The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated off, acidified with phosphoric acid and the organic phase was washed neutral with water to remove the solvent.

Relative viscosity: 1.297 Glass transition temperature: 208 ° C. Example B.9 15.5 g (0.05 mol) of bisphenol of example (A.1), 17.6 g (0.05 mol) of (4,4′-dihydroxytetraphenylmethane and 24.0 g (0.6 mol) of NaOH are dissolved with stirring in 411 ml of water in an inert gas atmosphere, and 0.516 g of 4-OH dissolved in 308 ml of methylene chloride.
(1,1,3,3-tetramethylbutyl) -phenol is added. 19.8 g of phosgene are introduced into a thoroughly stirred solution at pH 13-14 and at a temperature of 20-25 ° C. Five minutes after the introduction is completed, 0.1 ml of N-ethylpyridine is added.
The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated off, acidified with phosphoric acid and the organic phase was washed neutral with water to remove the solvent.

Relative viscosity: 1.218 Glass transition temperature: 212 ° C. Example B.10 18.3 g (0.05 mol) of bisphenol of Example (A.4) and 23.6 g (0.42 mol) of KOH were added in an inert gas atmosphere for 10 minutes.
Dissolve in 0 ml of water with stirring. Then 100 ml of methylene chloride are added. 17.3 g of phosgene are introduced into a stirred solution at pH 13-14 and at a temperature of 20-25 ° C. Five minutes after the introduction is completed, 0.3 ml of N-ethylpyridine is added. The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated off, the organic phase was acidified with phosphoric acid, washed with water until neutral and the solvent was removed.

Relative viscosity: 1.310 Glass transition temperature: 241 ° C. Example B.11 29.6 g (0.1 mol) of bisphenol of Example (A.5) and 24.0 g (0.6 mol) of NaOH were mixed in an inert gas atmosphere at 37 ° C.
Dissolve in 0 ml of water with stirring. Then 0.413 g of 4- (1,1,3,3-tetramethylbutyl) phenol in 277 ml of methylene chloride was added and the solution was stirred thoroughly at pH 13-14 and at a temperature of 20-25 ° C. 17.3 g of phosgene are introduced therein. Five minutes after the introduction was completed, 0.1 ml of N-
Add ethyl pyridine. The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated, the organic phase was acidified with phosphoric acid, washed with water until neutral,
The solvent was removed.

Relative viscosity: 1.370 Glass transition temperature: 193 ° C. Example B.12 62.0 g (0.2 mol) of bisphenol A.1, 182.4 g (0.
8 mol) of bisphenol A and 240 g (6 mol) of NaOH
Are dissolved in 2400 ml of water with stirring in an inert gas atmosphere. Then 6.603 g dissolved in 2400 ml of methylene chloride
Of 4- (1,1,3,3-tetramethylbutyl) phenol is added. 17.3 g of phosgene are introduced into a stirred solution at pH 13-14 and at a temperature of 20-25 ° C. Five minutes after the introduction is complete, 1 ml of N-ethylpyridine is added. The mixture is allowed to react for 45 minutes. After separating the aqueous phase containing no bisphenolate and acidifying the organic phase with phosphoric acid,
After washing with water until neutral, the solvent was removed.

Relative viscosity: 1.298 Glass transition temperature: 172 ° C. Example B.13 170.5 g (0.55 mol) of bisphenol of Example (A.3), 102.6 g (0.45 mol) of bisphenol A and 240 g
(6 mol) of NaOH are dissolved in 2400 ml of water with stirring in an inert gas atmosphere. Then 5.158 g of 4- (1,1,3,3-tetramethylbutyl) phenol in which 2400 ml of methylene chloride are dissolved is added. pH 13-14, and temperature 20-
198 g of phosgene are introduced into the solution, which is thoroughly stirred at 25 ° C. Five minutes after the introduction is complete, 1 ml of N-ethylpyridine is added. The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated off, the organic phase was acidified with phosphoric acid, washed with water until neutral and the solvent was removed.

Relative viscosity: 1.302 Glass transition temperature: 203 ° C. Example B.14 108.5 g (0.35 mol) of bisphenol of Example (A.1), 148.2 g (0.65 mol) of bisphenol A and 240 g
(6 mol) of NaOH are dissolved in 2400 ml of water with stirring in an inert gas atmosphere. Then 6.189 g of 4- (1,1,3,3-tetramethylbutyl) phenol dissolved in 2400 ml of methylene chloride are added. pH 13-14 and temperature 20-25
198 g of phosgene are introduced into the solution which has been thoroughly stirred at 0 ° C. Five minutes after the introduction is complete, 1 ml of N-ethylpyridine is added. The mixture is allowed to react for 45 minutes. The aqueous phase free of bisphenolate was separated off, the organic phase was acidified with phosphoric acid, washed with water until neutral and the solvent was removed.

Relative viscosity: 1.305 Glass transition temperature: 185 ° C To evaluate the UV stability of the new polycarbonate, use a mercury lamp (edge, filter 305 nm)
The production of primary free radicals under irradiation was measured in comparison to a polycarbonate based on 2,2-bis- (4-hydroxyphenyl) -propane. The polycarbonate of Example B.1 has a low rate of primary free radical generation, indicating a high UV stability.

The present invention provides a) a) at least 10,000, preferably 10,000 to 300,00
0, and more preferably the product mixture has a _w value (weight average molecular weight) of 20,000 to 80,000 when used in the manufacture of injection molded articles, and has the formula (1a) Wherein X, R ¹ , R ² , R ³ , R ⁴ and m are as defined in formula (I), wherein a bifunctional carbonate structural unit corresponding to 100 mol% to 2 mol%, based on the total amount of the structural units of the basic carbonate as 100 mol%
Preferably in an amount of 100 mol% to 5 mol%, more preferably in an amount of 100 mol% to 10 mol%, and most preferably in an amount of 100 mol% to 20 mol%. B) 99.6% to 0.1%, preferably 99% to 2% and more preferably 97.5% to 10% by weight of the elastomer or component a) of high molecular weight, thermoplastic, aromatic polycarbonate; Thermoplastics other than polycarbonates.

Particularly preferred polycarbonates (a) have the formula (Ia) wherein m is 4 or 5, and more preferably the formula (Ic) Wherein R ¹ and R ² are as defined in formula (Ia) but are preferably hydrogen, having a structural unit corresponding to

Other thermoplastics suitable as component (b) in the present invention are b1) amorphous thermoplastics, preferably having a glass temperature above 40 ° C., in particular in the range from 60 ° C. to 220 ° C .; 2.) Both partially crystalline thermoplastics, preferably having a melting point above 60 ° C., and more preferably in the range from 80 ° C. to 400 ° C.

The elastomer of component b) of the mixture according to the invention has b3) less than 9 ° C, preferably less than -10 ° C and more preferably less than 15 ° C.
It is a polymer having a glass temperature in the range of from 0 ° C to -140 ° C.

Examples of other amorphous thermoplastics are polycarbonates, polyesters, polyester carbonates, polyamides, polyolefins, polysulfones, polyketones, thermoplastic vinyl polymers such as polymethyl acrylate,
Or a homopolymer of an aromatic vinyl compound, a copolymer or rubber of an aromatic vinyl compound, polyether, polyimide,
And amorphous polymers consisting of a class of graft polymers of vinyl monomers onto thermoplastic polyurethane.

Examples of crystalline thermoplastics b2) are aliphatic polyesters, polyarylene sulfides, and partially crystalline examples of thermoplastics are given in b1) above.

Examples of elastomers b3) are various rubbers, for example ethylene-propylene hom, polyisoprene, polychloroprene, polysiloxane, random polypropylene, diene, olefin and acrylic rubber and natural rubber, strain-butadiene block copolymer, ethylene With vinyl acetate or (meth) acrylate, b
Elastic polyurethanes and elastic polycarbonate-polyether block copolymers unless indicated as thermoplastics in section 1) or b2).

Amorphous thermoplastics b1) are in particular polycarbonates other than the polycarbonates according to German Patent Application P 3,832,396.6. These other polycarbonates may be both homogeneous polycarbonates and also copolymerized polycarbonates, and may be both linear or branched. A particularly preferred bisphenol for polycarbonate is bisphenol A [= 2,2-bis- (4-hydroxyphenyl) -propane].

These other thermoplastic polycarbonates are known.

The molecular weight _w (weight average molecular weight as determined by gel permeation chromatography in tetrahydrofuran) of other thermoplastic polycarbonates is in the range of 10,000 to 300,000, preferably in the range of 12,000 to 150,000.

The other thermoplastic polycarbonates can be used both alone and in a mixture with component b) of the mixture according to the invention.

Other thermoplastics suitable as component b) for the preparation of the mixtures according to the invention are also aliphatic, thermoplastic polyesters, more preferably polyalkylene terephthalates, ie, for example, ethylene glycol, propane-
1,3-diol, butane-1,4-diol, hexane-
1,3-diol and 1,4-bis-hydroxymethylcyclohexane.

The molecular weight of these polyalkylene terephthalates (
_w ) is in the range of 10,000 to 80,000. Polyalkylene terephthalates can be obtained from dialkyl terephthalate and the corresponding diol by known methods, such as transesterification (see, for example, US Pat. No. 2,647,88).
No. 5, 2,643,989, 2,534,028, 2,578,660, 2,742,
No. 494, 2,901,466). These polyesters are known.

Other suitable thermoplastics also include thermoplastic polyamides.

Suitable thermoplastic polyamides are any partially crystalline polyamides, in particular polyamide-6, polyamide-6,6 and partially crystalline copolymerized polyamides based on these two components. Other suitable thermoplastic polyamides are those in which the acid component is completely or partially, especially adipic acid or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid Acid and / or adipic acid and / or caprolactam of cyclohexanecarboxylic acid and the diamine component is completely or partially, especially m
-And / or p-xylylenediamine and / or tetramethylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine and / or Or partially crystalline polyamides consisting of 1,4-diaminobutane, the composition of which is known in principle from the prior art (for example Encyclopedia of Polymers, Vol. 11 ) , P. 315 et seq.).

Other suitable thermoplastic polyamides are partially crystalline polyamides made entirely or partially from lactams containing 6 to 12 carbon atoms, optionally using one or more of the above-mentioned starting components. .

Particularly preferred partially crystalline polyamides are polyamide-6, polyamide-6,6 or copolymerized polyamides containing small amounts (up to about 10% by weight) of other copolymerizable components.

Suitable polyamides are, for example, hexamethylenediamine, decamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, m- or p-xylenediamine, bis- (4-aminocyclohexyl) -methane A mixture of 4,4'- and 2,2'-diaminodicyclohexylmethane, 2,2-bis- (4-aminocyclohexyl) -propane, a mixture of 4,4'- and 2,2'-diaminodicyclohexylmethane, 2-bis- (4-aminocyclohexyl) -propane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-aminoethyl-3,5,5-trimethylcyclohexylamine, 2,5-bis- (Aminomethyl) -norbornane, 2,6-bis- (aminoethyl) -norbornane, 1,4-diaminocyclohexane,
And diamines such as mixtures of these diamines, for example, oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, Amorphous polyamides obtained by polycondensation with isophthalic and terephthalic acids and mixtures of these dicarboxylic acids. Accordingly, amorphous copolyamides obtained by polycondensation of some of the above-mentioned diamines and / or dicarboxylic acids are also included. ω- such as ω-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid
Also included are amorphous copolyamides made with aminocarboxylic acids or their lactams.

Particularly suitable amorphous, thermoplastic polyamides are isophthalic acid, hexamethylenediamine and 4,4'-diaminidicyclohexylmethane, isophoronediamine, 2,2,4-
And 2,4,4-trimethylhexamethylenediamine, 2,5-
Polyamides obtained from other diamines such as and / or 2,6-bis- (aminomethyl) -norbornene; polyamides obtained from isophthalic acid, 4,4'-diaminidicyclohexylmethane and ω-caprolactam; Polyamides obtained from isophthalic acid, 3,3-dimethyl-4,4'-diaminodicyclohexylmethane and ω-laurinlactam; and terephthalic acid and 2,2,4- and 2,4,4-trimethylhexamethylenediamine Polyamide obtained from a mixture of isomers.

Instead of using pure 4,4'-diaminodicyclohexylmethane, 70 to 99 mol% of 4,4'-diamino isomer, 1 to 30 mol% of 2,4'-diamino isomer, 0 to 2 mol It is also possible to use a mixture of the positional isomers of diaminodicyclohexylmethane, consisting of a% of the 2,2'-diamino isomer and the corresponding highly condensed diamine optionally obtained by hydrogenation of industrial grade diaminodiphenylmethane. is there.

Suitable thermoplastic polyamides may consist of a mixture of partially crystalline and amorphous polyamides in which the amorphous polyamide component is less than the partially crystalline polyamide component. Amorphous polyamides and methods for their production are well known from the prior art (see, for example, Ullmann, Encyclopedia of Industrial Chemistry, Vol. 19, p. 50).

Another suitable thermoplastic b) is the so-called "LC polymer". Polymers referred to as LC polymers are polymers that can form liquid crystal melts. “Thermotopic
This type of polymer, also described as "tropic)"
Many have been disclosed (eg European Patent Publication EP
-A Nos. 0,131,845, 0,132,637 and 0,134,959). The above references further mention literature and also describe methods for measuring the liquid crystal state of polymer melts.

"LC polymers" include, for example, aromatic polyesters based on optionally substituted p-hydroxybenzoic acid, optionally substituted iso- and / or terephthalic acid, 2,7-dihydroxynaphthalene and other diphenols ( EP-A 0,131,84
No. 6), aromatic polyesters based on optionally substituted p-hydroxybenzoic acid, diphenol, carbonic acid and optionally aromatic dicarboxylic acid (EP-A No. 0,132,637) and optionally substituted p-hydroxybenzoic acid , 3-chloro-4-
Aromatics based on hydroxybenzoic acid, isophthalic acid, hydroquinone and 3,4'- and / or 4,4'-dihydroxydiphenyl ether and / or 3,4'- and / or 4,4'-dihydroxydiphenyl sulfide Polyester (EP-A No. 0,134,959).

The LC polymer is 18 to 1300Å at room temperature, preferably 25 to
It has a persistence length of 300 ° and especially 25 to 150 °.

The sustained length of a polymer at room temperature is determined by the average convolution of molecular chains in a dilute solution under (1) conditions (eg, PJ Flory “Principles of Polymer Chemistry [Princip
les of Polymer Chemistry], Cornell University Press, Ithaca, New York, NY) and characterizes half the step length of Kuhn. It can be measured by various methods, for example, light scattering and X-ray small angle measurement.
With a suitable sample, the persistence length can be measured in solids using small angle neutron scattering. Further theoretical and experimental methods are described, for example, by SH Wendorff, "Liquid crystal alignment in polymers (Lipuid Crystalline O.D.).
rder in Polymers) ", A. Bloomstein [Blumst
ein], Academic Press, 197
8, pages 16 and below, and “SM Aharoni, Mac
romolecules 19, (1986), pages 429 et seq.

Other suitable thermoplastics also include aromatic polyester carbonates.

The aromatic polyesters and polyester carbonates which can be used as thermoplastics b) according to the invention comprise at least one aromatic bisphenol, for example a compound of the formula (VII), at least one aromatic dicarboxylic acid and optionally carbonic acid. ing. Suitable aromatic dicarboxylic acids include, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid,
3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4 '
-Benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 2,2-bis- (4-carboxyphenyl)-
Propane and trimethyl-3-phenylindane-4,
5'-dicarboxylic acid.

Of the aromatic dicarboxylic acids, terephthalic acid and / or isophthalic acid are particularly preferably used.

Aromatic polyesters and polyester-carbonates are
It can be produced by methods of the type known from the literature for the production of polyesters or polyestercarbonates, for example by the method in homogeneous solution, by the transesterification in the melt, and by the two-phase interface method. .
The transesterification in the melt and especially the two-phase interface method are preferably used.

Transesterification methods (acetate method and phenyl ester method) of melts are described, for example, in U.S. Pat. Nos. 3,494,885 and 4,38.
6,186, 4,661,580, 4,680,371 and 4,680,372 and European Patent Publication EP-A 26,120, 26,121,
26,684, 28,030, 39,845, 91,602, 97,970,
79,075, 146,887, 156,103, 234,913, 234,919
No. 240,301 and DE-OS 1,495,
No. 626 and 2,232,977. The two-phase interface method is described, for example, in EP-A-68,014, 88,322.
Nos. 134,898, 151,750, 182,189, 219,708, 27
No. 2,426, German Patent Publication DE-OS No. 2,949,024,
3,007,934, 3,440,020 and Polymer Review, 10 "Condensation Polymers by Interfacial and Sol
ution) ", Paul. W. Morgan, Interscience Publishers
ublishers), New York 1965, Chapter VIII, page 325, polyester.

In the acetic ester method, bisphenol diacetate is generally used, and in the phenyl ester method, generally, bisphenol, an aromatic dicarboxylic acid or a diphenyl ester of an aromatic dicarboxylic acid and optionally diphenyl carbonate are accompanied by elimination of phenol, and optionally CO _2. Is used to produce polyester or polyester carbonate with elimination of In the two-phase interface method, the starting materials used in the production of polyesters and polyester carbonates are generally alkali metal phenolates, aromatic dicarboxylic dichlorides and optionally phosgene. In this condensation process, polyesters and polyester carbonates form with the formation of alkali metal chlorides.
Generally, the resulting salt dissolves in the aqueous phase, while the resulting polyester or the resulting polyester carbonate is present in solution in the organic phase and isolated therefrom.

Other suitable thermoplastics also include thermoplastic, linear or branched polyarylene sulfides.
They have the general formula In the above formula, R ₁ to R ₄ may be individually the same, and C ₁ -C ₆
Having a structural unit corresponding to, which represents alkyl, phenyl or hydrogen. The polyarylene sulfide may also contain diphenyl units.

Polyarylene sulfides and methods for their production are known (see, for example, US Pat. No. 3,354,129, EP-A-0,171,021).

Another suitable thermoplastic b) is a thermoplastic polyarylene sulfone.

Suitable polyarylene sulfones have an average weight average molecular weight
_w (determined by light scattering in CHCl ₃ ) is in the range of 1,000 to 200,000 and preferably 20,000 to 60,000. By way of example, 4,4'-dichlorophenylsulfone and bisphenols, in particular 2,2-bis-
2, obtained from (4-hydroxyphenyl) -propane
There are polyarylene sulfones having an average weight average molecular weight _w of 000 to 200,000.

These polyarylene sulfones are known (for example, US Pat. No. 3,264,536, DE-AS No. DE-AS).
1,794,171, UK Patent 1,264,900, U.S. Patent 3,64
No. 1,207, European Patent Publication EP-A-038,028,
DE-OS 3,601,419 and 3,601,42
No. 0). Suitable polyarylene sulfones may also be branched in known manner (for example, from DE-A-
DE-OS No. 2,305,413).

Other suitable thermoplastics b) are also polyphenylene oxides, suitable poly- (2,6-dialkyl-1,4-)
Phenylene oxide). Suitable polyphenylene oxides for the purposes of the present invention are from 2,000 to 100,000, preferably
It has a weight average molecular weight _w of 20,000 to 60,000 (measured by light scattering in chloroform). These polyphenylene oxides are known.

Suitable poly- (2,6-dialkyl-1,4-phenylene oxides) are known in the art by oxidative condensation of 2,6-dialkylphenols with oxygen in the presence of a copper salt and tertiary amine complex catalyst. (For example, DE-OS 2,126,434 and U.S. Pat.
3,306,875).

Suitable poly- (2,6-dialkyl-1,4-phenylene oxides) are in particular, for example, poly- (2,6-dimethyl-1,4-
Poly- [2,6-di- (C
₁ -C ₄ - alkyl) 1,4-phenylene oxide.

Other suitable thermoplastics b) also include aromatic polyether ketones (for example British Patent 1,078,234).
No. 4,010,147 and European Patent Publication EP-OS 0,135,938).

These are the following repeating structural elements: -O-E-O-E'- wherein -E'- is a residue of a bisarylketone having two bonds, and -O-E-O- is a two-bond Diphenolate residues having a hand, they are, for example, according to GB 1,078,234, dialkali diphenolates having the formula alkali-OEO-alkali and bis- (haloaryl having the formula halogen-E'-halogen ) -Ketone.
One suitable dialkali diphenolate is for example 2,2-
From bis- (4-hydroxyphenyl) -propane, a suitable bis- (haloaryl) -ketone is 4,4-dichlorobenzophenone.

Other suitable thermoplastics b) also include thermoplastic vinyl polymers.

It is a homopolymer of a vinyl compound of a vinyl polymer, a copolymer of a vinyl compound, and a graft polymer of a vinyl polymer on rubber in the meaning of the present invention.

Suitable homopolymers and copolymers for the purposes of the present invention are styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, C ₁ -C ₁₂ (cyclo) alkyl esters of (meth) acrylic acid, C ₁ -C ₄ A polymer of vinyl carboxylate, the copolymer of which can also be obtained from mixtures of these vinyl compounds by known methods.

The homopolymer or copolymer must have an intrinsic viscosity of 0.3 to 1.5 dl / g (measured in a known manner at 23 ° C. in toluene).

Suitable vinyl polymers such as thermoplastic poly -C ₁ -C ₄ -
Alkyl methacrylates, for example methyl, ethyl, propyl or butyl methacrylate, preferably methyl or ethyl methacrylate. Both homopolymers and copolymers of these methacrylates are included. Furthermore, other ethylenically unsaturated, copolymerizable monomers such as (meth) acrylonitrile, (α-methyl) styrene, bromostyrene, vinyl acetate, C ₁ -C ₈ -alkyl acrylate, (meth) acrylic acid Ethylene, propylene and N-
Vinylpyrrolidone can also be copolymerized in small amounts.

Suitable thermoplastic poly-C ₁ -C ₄ -alkyl methacrylates for the purposes of the present invention are known in the literature or can be obtained by methods known from the literature.

Suitable vinyl polymers include copolymers of styrene or α-methylstyrene and acrylonitrile, optionally including up to 40% by weight of esters of acrylic or methacrylic acid, especially methyl methacrylate or n-butyl acrylate. The styrene derivative must always be present as a monomer. The styrene derivative is present in a proportion of 100 to 10% by weight, preferably 90 to 20% by weight, and more preferably 80 to 30% by weight, such as free radical polymerization in bulk, solution, suspension or emulsion. It can be obtained by any standard method, but preferably by free radical emulsion polymerization in water.

Suitable graft polymers have a glass transition temperature of 0 ° C. or less,
It is formed by the polymerization of the vinyl monomers or mixtures of vinyl monomers mentioned above, preferably in the presence of a rubber below -20 ° C. Graft polymer is generally 1-85% by weight
And preferably from 10 to 80% by weight of rubber. The graft polymer can be produced in solution, bulk or emulsion, preferably in emulsion. A mixture of vinyl monomers can be graft polymerized simultaneously or sequentially.

Suitable rubbers are preferably diene rubbers and acrylate rubbers.

Diene rubber, for example polybutadiene, polyisoprene and butadiene and up to 35% by weight of styrene, acrylonitrile, a copolymer of comonomers such as methyl methacrylate and C ₁ -C ₆ alkyl acrylates.

The acrylate rubber may optionally contain up to 15% by weight of other unsaturated monomers such as styrene, methyl methacrylate, butadiene, vinyl methyl ether, acrylonitrile, and at least one such as divinylbenzene,
Glycol-bis-acrylate, bis-acrylamide, triallyl ether phosphate, triallyl citrate, allyl esters of acrylic acid and methacrylic acid,
Were mixed with polyfunctional crosslinking agents such as triallyl isocyanurate, C ₁ -C ₆ - alkylinylalkenyl acrylates, in particular C ₂ -
C ₆ - crosslinked alkyl acrylate, an emulsion polymer of the particulate, acrylate rubber contains up to 4 wt.% Of a crosslinking agent comonomers.

Mixture of diene rubber and acrylate rubber and also core
Rubbers having a sheath structure are also suitable for the production of graft polymers.

In the case of graft polymerization, the rubber must be present in divided particles, for example as latex. These particles generally have an average particle size of 10 nm to 2000 nm.

The grafted polymer is free-radical emulsification of vinyl monomers in the presence of a rubber latex at a temperature of 50 to 90 ° C. using known methods, for example using aqueous initiators such as peroxydisulfate or redox initiators. It can be produced by graft polymerization.

80 to wt% or more of gel content and 80 have an average particle size of 800nm (d _50). Emulsion graft polymers prepared by free radical graft polymerization on particulate highly crosslinked rubbers (dienes or alkyl acrylate rubbers) are preferred.

 Industrial ABS polymers are particularly suitable.

Also suitable are vinyl homopolymers and / or mixtures of graft and vinyl polymers.

Other suitable thermoplastics b) include thermoplastic polyurethanes. These are the reaction products of diisocyanates, wholly or predominantly aliphatic oligo- and / or poly-esters and / or ethers with one or more chain extenders. These thermoplastic polyurethanes are linear in nature and have thermoplastic processing properties.

Thermoplastic polyurethanes are known and can be obtained by known methods (for example, US Pat. No. 3,214,411; JH Saunders and KC Frisch)
“Polyurethanes, Chemistry and Technology
y and Technology) ", Vol. II, pp. 299-451, Intea Science Publishers, New York, 19
64; and Mobay Chemical, "A
Processing Handbook for Texin Urethane Elastoplas
tic Materials ", Pittsburgh, PA.

Starting materials for the production of oligoesters and polyesters are, for example, adipic acid, succinic acid, suberic acid sebacate, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid and isophthalic acid.

 Adipic acid is preferred.

Suitable glycols for the production of oligoesters and polyesters are, for example, ethylene glycol, 1,2- and 1,3-
Propylene glycol, butane-1,2-,-1,3-,-1,
4-, -2,3- and -2,4-diol, hexanediol, bis-hydroxymethylcyclohexane, diethylene glycol and 2,2-dimethylpropylene glycol. Further small amounts, ie, up to 1 mol% of trihydric or polyhydric alcohols such as trimethylolpropane, glycerol, hexanetriol and the like can be used with glycols.

The resulting hydroxy oligoester or polyester has a molecular weight of at least 600, a hydroxyl number of about 25 to 190, and preferably about 40 to 150, an acid number of about 0.5 to 2, and a water content of about 0.01 to 0.2%. I have.

Oligoesters and polyesters may also be oligomeric or polymeric lactones such as, for example, oligocaprolactone or polycaprolactone, and polybutene-
It includes aliphatic polycarbonates such as 1,4-diol carbonate or polyhexane-1,6-diol carbonate.

Oligoesters particularly suitable as starting materials for thermoplastic polyurethanes are prepared from adipic acid and glycols containing at least one primary hydroxyl group. Acid value
The condensation is terminated when it reaches 10, and preferably about 0.5 to 2. The water formed during the reaction has a final moisture content of about 0.
It is fractionated simultaneously or later to be between 01 and 0.05%, and preferably between 0.01 and 0.02.

Oligoethers or polyethers for the production of thermoplastic polyurethanes are based, for example, on tetramethylene glycol, propylene glycol and ethylene glycol.

Polyacetal is regarded as or like polyether and is used as such.

600 to 2,000 for oligoethers or polyethers,
And preferably has an average molecular weight _w (number average determined by the OH number of the product) of 1,000 to 2,000.

4,4'-Diphenylmethane diisocyanate is preferably used as an organic diisocyanate in the production of polyurethanes. It must contain less than 5% of 2,4'-diphenylmethane diisocyanate and less than 2% of dimers of diphenylmethane diisocyanate. Furthermore, the acidity expressed by HC1 is about 0.005 to 0.2%
Must be in the range. The acidity, expressed as HC1%, is the standard for extracting chloride from isocyanate in hot aqueous methanol solution or liberating chloride by hydrolysis with water and determining the concentration of chloride ions present therein. It is determined by titrating the extract with a silver nitrate solution.

For the production of thermoplastic polyurethanes, for example, ethylene, propylene, butylene, cyclo-1,3-pentylene, cyclo-1,4-hexylene, cyclo-1,2-hexylene, 2,4
Diisocyanates of tolylene, 2,6-tolylene, p-phenylene, n-phenylene, xylylene, 1,4-naphthylene, 1,5-naphthylene, 4,4'-diphenylene; 2,2-
Diphenylpropane-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1-chloro-2,
4-diisocyanate, furfuryl diisocyanate,
Dicyclohexylmethane diisocyanate, isophorone diisocyanate, diphenylethane diisocyanate and bis-glycols such as ethylene glycol and butanediol
It is also possible to use other diisocyanates, including (isocyanatophenyl) -ether.

Suitable chain extenders are organic difunctional compounds containing active hydrogens which react with isocyanates, such as diols, hydroxycarboxylic acids, dicarboxylic acids, diamines and alkanolamines and water. Examples of such chain extenders are
For example, ethylene, propylene and butylene glycol,
Butane-1,4-diol, butanediol, xylylene glycol, amylene glycol, 1,4-phenylene-
Bis-β-hydroxyethyl ether, 1,3-phenylene-bis-β-hydroxyethyl ether, bis- (hydroxymethylcyclohexane), hexanediol,
Adipic acid, ω-hydroxycaproic acid, thiodiglycol, ethylenediamine, propylene, butylene, hexamethylene, cyclohexylene, phenylene, tolylene and xylylenediamine, diaminodicyclohexylmethane, isophoronediamine, 3,3′-dichlorobenzidine, 3,3'-dinitrobenzidine, ethanolamine, aminopropyl alcohol and p-aminobenzyl alcohol. The molar ratio of the oligoester or polyester to the bifunctional chain extender ranges from 1: 1 to 1:50 and preferably from 1: 2 to 1:30.

In addition to the difunctional chain extender, a trifunctional or trifunctional or higher functional chain extender is used in an amount as small as up to about 5 mol%, based on the number of moles of the bifunctional chain extender used. It is also possible.

Examples of trifunctional or more than trifunctional chain extenders are glycerol, trimethylolpropane, hexanetriol, pentaerythritol and triethanolamine.

Monofunctional components, such as butanol, can also be used in the production of thermoplastic polyurethanes.

All of the diisocyanates, oligoesters, polyethers, chain extenders and monofunctional components mentioned as structural units of the thermoplastic polyurethane are known in the literature or can be obtained by methods known in the literature.

Known processes for producing polyurethanes are carried out, for example, as follows: For example, oligoesters or polyesters, organic diisocyanates and chain extenders are preferably used at about 50 to 220 ° C.
, And then mixed. The oligoester or polyester is preferably first individually heated, then mixed with the chain extender, and the resulting mixture is mixed with the preheated isocyanate.

The starting components for the production of the polyurethane can be mixed by any mechanical stirrer that gives a strong mixing in a short time. If the viscosity of the mixture rises too quickly during mechanical stirring, lower the temperature to reduce the reaction rate or use a small amount (from 0.001 to 0.05
% By weight) of citric acid or the like may be added. To increase the reaction rate, a suitable catalyst may be used, such as, for example, the tertiary amines mentioned in U.S. Pat. No. 2,729,618.

Examples of elastomers b3) include ethylene / propylene rubber, polyisoprene, polychloroprene, polysiloxane, atactic polypropylene, dienes, olefins and acrylate rubbers and various rubbers such as natural rubber, styrene / butadiene block copolymers, ethylene And vinyl acetate or (meth) acrylate, elastic polyurethane, elastic polycarbonate polyether block copolymer and polyester polyether block copolymer.

Essentially at least two of the following monomers: chloroprene, butadiene, isoprene, isobutene, styrene,
Copolymers with elastic properties, obtained from acrylonitrile, ethylene, propylene vinyl acetate and (meth) acrylates having 1 to 18 carbon atoms in the alcohol component, ie, for example, the "methods of organic chemistry"
der Orgabnischen Chemie ", Houben-Weyl, Volume 14/1, Georg Thieme
Thieme), Stuttgart, 1961,
On pages 393-403, and CB Bucknall,
Polymers of the type described in "Toughened Plastics", Science Publishers, London, 1977-especially graft copolymers (graft rubbers)
It is preferred to use-.

By way of example, it has from 15 to 45% by weight of vinyl acetate units and is non-fluid or non-fluid, measured at 190 ° C. according to DIN 53735.
There are ethylene / vinyl acetate copolymers having a melt index of 1000, preferably 0.1 to 20, and a load bearing capacity of 2.16 kp.

The following may also be mentioned: the weight ratio of ethylene to propylene residues is from 40:60 to 90:10, preferably 40:60.
So-called EPM or EPDM rubber in the range from 65 to 35:35.

Mooney viscosity of non-crosslinked EPM or EPDM rubber (ML _{1 +} 4/100
C) is between 25 and 100, and preferably between 35 and 90. The gel content of the uncrosslinked EPM or EPDM rubber is less than 1% by weight.

The ethylene / propylene copolymer (EPM) used contains virtually no double bonds,
Diene terpolymers contain from 1 to 20 double bonds per 1000 C atoms. For example, the following may be mentioned as suitable diene monomers: conjugated dienes such as isoprene and butadiene, and for example 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5 −
Non-conjugated dienes having from 5 to 25 C atoms such as dimethyl-1,5-hexadiene and 1,4-octadiene; cyclic dienes such as cyclopentadiene, cyclohexadiene, cyclooctadiene and dicyclopentadiene; Alkenyl norbornenes such as ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene, and, for example, 3-methyl-
Tricyclodienes such as tricyclo- (5,2,1,0,2,6) -3,8-decadiene. Non-conjugated dienes, 1,5-hexadiene, ethylidene norbornene and dicyclopentadiene may be preferred. The diene content in EPDM is preferably from 0.5 to 10% by weight.

Such EPM or EPDM rubber is known from DE-OS
No. 2,808,709.

 The following are also suitable as elastomers C):
Y- of vinyl aromatic monomer (X) and conjugated diene (Y)
Partially hydrogenated block copolymers of the Y-form. this
These block copolymers can be produced by known methods.
(For example, Kraton G manufactured by Shell)
).

It is generally used for the production of styrene / diene block copolymers and is referred to as “Encyclopedia of Polymer Science and Technology”.
Polymer Science and Tschnology ", Vol. 15, Interscience, New York (1971), p. 508 et seq. Describes conjugates such as styrene, alpha-methylstyrene and / or vinyltoluene and butadiene and / or isoprene. It can be utilized for the preparation of suitable XY block copolymers of dienes.Selective hydrogenation means that the ethylenic double bond is virtually completely hydrogenated, but the aromatic double bond is essentially Not affected
It can be carried out by a method known per se.

Such selectively hydrogenated block copolymers are described, for example, in DE-OS 3,000,282.

Also suitable are: polybutadienes, butadiene / styrene copolymers and poly (meth) acrylates grafted with styrene and / or acrylonitrile and / or alkyl (meth) acrylates, such as styrene or alkylstyrene and conjugated dienes (resistant to Impact polystyrene), i.e. DE-OS 1,694,173
No. 3,564,077, polybutadienes grafted with acrylate or methacrylate, vinyl acetate, acrylonitrile, styrene and / or alkyls, butadiene / styrene or butadiene / acrylonitrile copolymers Or polyisobutene or polyisoprene, ie DE-OS 2,348,377 (= U.S. Pat. No. 3,919,353)
Or those of the type described in DE-OS No. 3,105,364 and DE-OS No. 3,019,233.

Particularly suitable elastomers are for example German Offenlegungsschrift
DE-OS 2,035,390 (= U.S. Patent No. 3,644,574) or D
ABS polymers of the type described in E-OS 2,248,242 (= British Patent 1,409,275) (both mixed and grafted).

In addition, the elastomer may be I. 10 to 40, preferably 10 to 35, in particular 15 to 25% by weight, based on the graft product, of at least one (meth) acrylate and / or 10 to 3 based on the mixture.
5, preferably 65 to 90, preferably 65 to 80% by weight, based on acrylonitrile and the mixture, preferably 20 to 35% by weight
Of styrene at least 7 based on II, which is the graft substrate.
A graft substrate obtained by carrying out a grafting reaction on 60 to 90, preferably 65 to 90, in particular 75 to 85% by weight of butadiene polymer, based on the graft product, containing 0% by weight of butadiene residues,
The gel content of II is ≧ 70% (measured in toluene), the degree of grafting G is between 0.15 and 0.55, and the average particle size d ₅₀ of the graft polymer C) is between 0.2 and 0.6, preferably Elastomers of 0.3 to 0.5 μm are most preferably used (for example, DE-OS 3,32).
4,398 and EP-A-56,243).

Particularly preferred elastomers are: a) 25 to 98% by weight, based on the graft product, having a glass transition temperature of -20 ° C. or less as the graft substrate
An acrylate rubber, and b) as a graft monomer, the homopolymer or copolymer should have a glass transition temperature greater than 25 ° C. if produced in the absence of (a), graft formation. 2 to 75% by weight, based on the weight of the polymer, of a graft polymer of at least one polymerizable ethylenically unsaturated monomer (see, for example, EP-A-50,265).

 In addition to the above elastomers, elastic polyurethanes (eg,
Texin ), Elastic polyester / polyester
-Tel block copolymer (for example, Hytrel [Hytrel]
) And elastic polycarbonate / polyether blocks
It is also possible to use copolymers. These elas
Tomers are known, for example, H.G. Elias,
Makulomolekule, Hutti
Huthig u.Wepf, Base
No. 4, 1981, p. 787 and A. Noshay and
J.E. McGrath, block copolymer (Block
 Copolymers), Academic Press New York
, 1977, p. 341.

Certain types of silicone graft rubbers described, for example, in DE-OS 3,629,763 are also suitable as elastomers to be used.

 These elastomers are known.

A mixture of polycarbonate a) and elastomer b3) can be prepared by mixing components a) and b3) in the melt in standard equipment such as, for example, a kneader, single screw or twin screw extruder or roll. .

The invention also relates to 0.1 to 99.9% by weight, preferably 1 to 98% by weight and more preferably 2.5 to 90% by weight of polycarbonate a) and 99.9 to 0.1% by weight, preferably 99 to 2% by weight and more Polycarbonate a), preferably comprising 97.5 to 10% by weight of elastomer b3), wherein polycarbonate a) is melted and elastomer b3) is added and homogenized in a melt of polycarbonate. And other thermoplastics
b1) or b2) may be prepared, for example, by mixing the solutions of components a) and b) or by mixing the components in a kneader, on a roll or in a single or multi-screw extruder. it can.

The invention also relates to 0.1 to 99.9% by weight, preferably 1 to 99% by weight and more preferably 2.5 to 90% by weight of polycarbonate a) and 99.9 to 0.1% by weight, preferably 99 to 2% by weight and more All the components, preferably 97.5 to 10% by weight of the other thermoplastics b1) or b2), are mixed in solution and the resulting mixture is processed in the usual way or The present invention relates to a method for producing a mixture, which comprises mixing and homogenizing in a melt. Additives commonly used for component b), such as fillers and / or components and / or
Alternatively, the fibers and / or lubricants and / or softeners and / or colorants can be added to the mixture as component c) in conventional amounts.

Inorganic fillers are ceramic fillers such as, for example, aluminum nitrite, silicate, titanium dioxide, talc, mica, carbon black; fibers are, for example, glass, carbon or liquid crystalline polymer fibers.

Examples of nucleating agents are barium sulfate and TiO _2.

These additives are incorporated in conventional amounts into component b) either before the preparation of the mixtures according to the invention or together with the polycarbonates of component a) or subsequently into the mixtures according to the invention of components a) and b). It can be added by such a method.

Similarly, the abovementioned additives can be added in conventional amounts to the polycarbonate of component a) before, during or after the mixture with component b).

The mixture according to the invention can be processed in a conventional manner in standard mixing equipment to form any type of shaped body.

The mixtures according to the invention are used for hub caps, dashboards and steering column casings for motor vehicles.
casing). For example, when high toughness is required at low temperature, such as for bumpers,
Spoilers and impact strips comprising an elastomer (component b3)) as a second component are advantageous.

It can be used as a mixture according to the invention or as a casing of a household appliance, as a multipoint connector and as a washing tub.

In particular, films can be produced from the mixtures according to the invention. The film has a preferred thickness of 1 to 1500 μm, and
It has a particularly preferred thickness of 10 to 900 μm.

The resulting film can be stretched in a known manner uniaxially or biaxially, preferably at a ratio of 1: 1.5 to 1: 3.

The film can be produced in a known manner for producing films, for example by extrusion of a polymer melt through a sheet die, by blowing in a film blower, by deep drawing or by casting. The latter is done by pouring a concentrated solution of the polymer in a suitable solvent onto a smooth substrate, evaporating the solvent and lifting the produced film from the substrate.

Depending on the component b) of the mixture and on the weight composition of the mixture of components a), b) and c), generally from 80 to
Films produced by extrusion at 450 ° C. are often biaxially stretched after cooling to at least 20 ° C. Films suitable for deep drawing can also be obtained by rolling a preformed film of a mixture of (a)), b) and c) at a temperature of up to about 290 ° C.

Cast films are obtained by pouring an optionally concentrated solution of the polymer mixture onto a smooth surface and evaporating the solvent at 25 to 290 ° C. In addition to parallel plane plates of material such as glass, ceramic, copper, etc., the smooth planes used are denser than the polymer solution and are liquid surfaces in which neither the polymer nor its solvent dissolves. You may.

The films according to the invention can be used on their own or in combination with films of other polymers.

Depending on the composition of the mixture and the choice of component b), and optionally c), it is highly transparent to light and a very uniform surface due to the choice of additional films for the composite film or the choice of components b) / c) It is possible to produce films with a structure, in particular a thickness of up to 1000 μm and even more particularly up to 800 μm. These films are easy to print,
There is scratch resistance.

The films according to the invention can be used as information carriers in many industrial fields. Examples of applications include monitoring and warning systems for automatic equipment and the home appliance (scalar)
e) Includes industrial and office machinery and electrical insulating films.

More specifically, the film can be used for any application requiring high heat resistance.

For some applications, it is advantageous to coat the film according to the invention with a protective lacquer. The film or composite film may be manufactured in the form of a homogeneous, composite or asymmetric membrane and used in a known manner. it can. The membrane, film or composite film is smooth and can form hollow articles of various geometric shapes-cylindrical, spherical or tubular-or can form hollow fibers. Such shaped articles can be manufactured by methods known to those skilled in the art.

The films according to the invention have a particularly high degree of dimensional stability under heating and are very selective but permeable to many gases. Therefore, it can be conveniently used for the gel permeation method.

Example C) Component C1) Corresponding to Example B1) C2) Polystyrene prepared by free-radical polymerization of styrene in a known manner, _w (measured by light scattering) 260,000 C3) Bisphenol-A-polycarbonate, relative viscosity η _rel (measured in CH ₂ Cl ₂ at 25 ° C. and C = 0.5 g / dl) 1.28 C4) Polymethyl methacrylate V811 (Rohm & Haas) C5) Polycaprolactam, relative viscosity 3.0 (in m-cresol) C6) Polyethylene terephthalate having an intrinsic viscosity of 0.72 measured at 25 ° C. in phenol / o-dichlorobenzene (weight ratio 1: 1) C7) Phenol / o-dichlorobenzene (weight ratio 1) 1) polybutylene terephthalate having an intrinsic viscosity of 1.21 measured at 25 ° C. in C8) Exso EPM rubber Exxelo
r) VA 1803 C9) 80 parts by weight of crosslinked butadiene (70% by weight in toluene
(The above gel content) and an emulsion polymer of a graft base comprising 18 parts by weight of methyl methacrylate and 2 parts by weight of n-butyl acrylate, wherein the average particle size of the graft base present in the latex is 0.3 to 0.4 μm. It is.

C10) Relative viscosity η _rel measured at 25 ° C in chloroform
(0.5% by weight solution) Poly (2,6-dimethyl-) having 1.62
1,4-phenylene) -ether C11) based on bisphenol A, having an ester content of 50% by weight (isophthalic acid: terephthalic acid = 1: 1), relative viscosity of 1.30 (0.5% by weight solution in methylene chloride) C13) An aromatic polycarbonate having a relative viscosity of 1.249 (0.5% by weight solution in methylene chloride) prepared by reacting dichlorodimethyl sulfone and bisphenol A in diphenyl sulfone according to known methods. C14) It is produced by reacting difluorobenzophenone and bisphenol A by a known method, and 1.
Bisphenol A based polyether ketone having a relative viscosity of 455 (0.5% by weight solution in methylene chloride) C15) Copolymer of styrene and acrylonitrile having an acrylonitrile content of 28% by weight prepared by emulsion polymerization C16) Corresponding to Example B13) C17) Corresponding to Example B14) C18) Corresponding to Example B7).

D) Mixture 37 g of D1) C1) and 37 g of C2) were each dissolved in 200 ml of methylene chloride. The solutions were then combined, and the solvent was partially removed in vacuo to leave a concentrated solution, producing a 200 μm thick film on a film draw bench. Six pieces of this film were placed on top of each other and pressed in air at 270 ° C. for 5 minutes under a pressure of 200 bar to form a rectangular laminate having a thickness of 1.042 mm.

D2) 30 g of C1) and 30 g of C2) were each dissolved in 200 ml of methylene chloride. The solutions were then combined and the solvent was concentrated as in D1) to produce a 210 μm thick film. Six pieces of this film were placed one on top of the other as in Example D1) and pressed in air at 250 ° C. for 5 minutes under a pressure of 210 bar to form a rectangular laminate of 0.989 mm thickness.

D3) 25 g of C1) and 25 g of C2) were each dissolved in 200 ml of methylene chloride. The solutions were then combined, and the solvent was partially removed in vacuo to leave a concentrated solution, producing a 200 μm thick film on a film stretching table. Six pieces of this film are placed on top of each other and placed at 270 ° C. under a pressure of 200 bar.
For 1 minute in air to form a rectangular laminate of 0.61 mm thickness.

D4) 70 g of C5) and 30 g of C1) are melted at a temperature of about 260 ° C to 280 ° C and homogenized in the flask. After the melt had cooled, the mixture was crushed and the granules were rolled to form 1.6 mm thick moldings in the same manner as described in Example D3).

D5) 35 g of C6) and B1) 15 g were rolled as described in Example D4) to form moldings 1.6 mm thick.

D6) Example D was prepared by mixing 60 g of the substance of C16) with 40 g of the substance of C7).
Rolling was performed as described in 4) to form a molded product having a thickness of 1.6 mm.

D7) Example D was prepared by mixing 40 g of the substance of C16) with 60 g of the substance of C7).
Rolling was performed as described in 4) to form a molded product having a thickness of 1.6 mm.

D8) Example D was prepared by mixing 60 g of the substance of C16) with 40 g of the substance of C6).
Rolling was performed as described in 4) to form a molded product having a thickness of 1.6 mm.

D9) 40 g of the substance of C16) are mixed with 60 g of the substance of C6),
Rolling was performed as described in 4) to form a molded product having a thickness of 1.6 mm.

D10) 80 parts by weight of the substance of C16) are homogenized together with 20 parts by weight of the substance of C8) in a twin-screw extruder at a temperature of 340 ° C., and molded into 80 × 10 × 4 mm test pieces in an ordinary injection molding machine. Injection molding.

D11) 80 parts by weight of the substance of C16) are homogenized together with 20 parts by weight of the substance of C9) in a twin-screw extruder at a temperature of 340 ° C., and molded into 80 × 10 × 4 mm test pieces in an ordinary injection molding machine. Injection molding.

D12) 70 g of the substance of C18) and 30 g of the substance of C11) are each dissolved in 400 ml of methylene chloride. Combine the solutions and remove the solvent almost completely in vacuo; make a 190 μm thick film from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a rectangular molded article having a thickness of 0.92 mm.

D13) Dissolve 30 g of the substance C18) and 70 g of the substance C11) in 400 ml of methylene chloride each. The solutions are combined and the solvent is almost completely removed in vacuo; a 200 μm thick film is produced from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a 1.0 mm thick rectangular molding.

D14) Dissolve 70 g of the substance C18) and 30 g of the substance C12) in 400 ml of methylene chloride each. The solutions are combined and the solvent is almost completely removed in vacuo; a 200 μm thick film is produced from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a rectangular molded article having a thickness of 0.98 mm.

D15) Dissolve 30 g of the substance C18) and 70 g of the substance C12) in 400 ml of methylene chloride each. The solutions are combined and the solvent is almost completely removed in vacuo; a 180 μm thick film is produced from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a rectangular molded article having a thickness of 0.8 mm.

D16) 70 g of the substance of C18) and 30 g of the substance of C10) are each dissolved in 400 ml of methylene chloride. Combine the solutions and remove the solvent almost completely in vacuo; make a 190 μm thick film from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a 1.05 mm thick rectangular molding.

D17) Dissolve 30 g of the substance C18) and 70 g of the substance C10) in 400 ml of methylene chloride each. The solutions are combined and the solvent is almost completely removed in vacuo; a 200 μm thick film is produced from the concentrated solution on a film coating table. Five pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a rectangular molded article having a thickness of 0.7 mm.

D18) 70 g of the material of C18) were mixed with 30 g of the material of C13) and rolled as described in Example D4) to form moldings 1.5 mm thick.

D19) 70 g of the material of C18) were mixed with 30 g of the material of C14) and rolled as described in Example D4) to form a 1.6 mm thick molding.

D20) Dissolve 60 g of the substance of C17) and 40 g of the substance of C15) in 400 ml of methylene chloride each. The solutions are combined and the solvent is almost completely removed in vacuo; a 200 μm thick film is produced from the concentrated solution on a film coating table. Six pieces of this film are placed one on top of the other and 270 ° C. under a pressure of 200 bar.
For 5 minutes in air to form a 1.0 mm thick rectangular molding.

E) Test of test specimens manufactured according to D: Shear modulus of test specimens Brabender type 802
It was measured above room temperature using a 301 torsion pendulum. 1K /
Heated at a heating rate of 1 min to the temperature indicated below, the specimen was exposed to a 10p tensile load throughout the measurement period. The torque was 1570 gcm ² . Since the specimens do not have sufficient internal strength, deformations of the specimens are clearly perceptible at elasticity values below 10 MPa.

F) Properties of the permeation behavior: Measurement of the permeability of the polymer membrane to gas (permeation) The permeation of gas through the impermeable polymer membrane is described by the dissolution / diffusion method. The characteristic constant of this method is given pressure difference Δ
In the case of p, the permeability coefficient P indicating the volume V of gas passing through a film of known surface area F and thickness d during a certain time t
It is. In the steady state, the following equation Can be induced. Furthermore, permeability depends on temperature and the moisture of the gas.

The measuring device consists of a two-chamber system regulated at a constant temperature. One chamber is designed to receive the test gas,
The other chamber is designed to receive the permeated gas. The two chambers are separated by the membrane to be measured.

Before introducing the gas, the two chambers are evacuated to 10 ⁻³ mbar and then the first chamber is filled with the gas. The permeated gas (inert gas) then causes an increase in the pressure of the fixed volume permeate chamber, and the increase in pressure as a function of time until gas passage reaches a steady state is measured by a pressure recorder (MKS Baratron [Baratro]).
n]). V is calculated by NTP. Scheduled pressure difference Δp taking into account external air pressure
It is adjusted to each case 10 ⁵ Pa. The film thickness d is measured by a micrometer as the average of 10 independent thickness measurements across the film surface.

From these values, the transmission coefficient P is calculated using the following dimensions. It is measured according to (I) with reference to a film thickness of 1 mm.

 The above measurement parameters are: Indian: 25 ± 1 ° C, Relative humidity: 0%.

G) Preparation of Films Example G1) 20 g of the polycarbonate corresponding to Example B2 and 50 parts by weight of polycarbonate and 50 parts by weight of an aromatic polyester based on bisphenol A and iso- / terephthalic acid (1: 1) 20 g of an aromatic polyester ester having a relative viscosity of 1.30 as measured in methylene chloride at 25 ° C.
Dissolve in 0 ml methylene chloride, combine the two solutions,
After concentration, a film having a pressure of about 150 μm was formed on a smooth glass plate. The film was dimensionally stable at 190 ° C. The film was dried in a vacuum at a temperature of 90 ° C. The transmission coefficient P was then measured: for O ₂ : 184.9 for CO ₂ : 1106.6 for N ₂ : 39.5 for CH ₄ : 42.3 This film was subjected to a relative viscosity of 1.28; a glass transition temperature of 150 ° C.
Bisphenol A polycarbonate combined with a 154 μm thick film at 210 bar pressure at about 200 ° C. for about 3
Rolled for minutes, to produce a composite film having a thickness of about 250 μm.

The composite film was still dimensionally stable at 190 ° C. Permeability coefficient P: relative O _2: relative 112.3 CO _2: relative 703.7 N _2: 31.4 (measured as described above).

Example G2) EP-PS 142,024, prepared according to Example 2 and measuring 120 P, measured at 306 ° C. and a shear rate of 1000 / sec.
15 g of poly p-phenylene sulfide having a melt viscosity of a · s, and also 15 g of component C1) (corresponding to Example B1)
Was prepared by mixing well in a small kneader at about 310 ° C. A film of about 403 μm thickness was rolled from the mixture at 280 ° C. under a pressure of 200 bar (pressing time: about 4 minutes).

From 100 ° C to 230 ° C the following permeation values (measured as described above) were obtained, while retaining heat resistance without a significant decrease in elasticity: For O ₂ : 27.1 For CO ₂ For: 114.3.

For comparison, the permeation values of O ₂ and CO ₂ were measured only for poly p-phenylene sulfide. A corresponding film was prepared from the described material by rolling at 280 ° C. for 4 minutes.

 The film had a thickness of 387 μm.

For O ₂ : 4.4 For CO ₂ : 18.6.

This film showed a distinct decrease in elasticity between 80 ° C and 150 ° C.

Example G3) Prepared on a film-coated table according to Example D3) and
The measured results of the transmission coefficient P of a film having a thickness of μm are as follows: for O ₂ : 21.1 for N ₂ : 2.7 for CH ₄ : 3.5 for CO ₂ : 94.2 film Was vinegar-stable up to about 160 ° C.

Example G4) The measurement results of the transmission coefficient P of a film produced according to Example D2) and having a thickness of 100 μm are as follows: for O ₂ : 136.9 For N ₂ : 27.4 CH ₄ In contrast: 39.1 for CO ₂ : 836.4 The film was vinegar-stable up to about 180 ° C.

Thus, the examples according to the invention illustrate the great advantages of the films according to the invention, namely high heat resistance and good transmission properties.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Guyenter Bymans Day 5090 Leif Elksen 1 Carl-Arnold-Schütlasse 4 (56) References JP-A-2-88634 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 69/00 C08L 21/00 CA (STN) REGISTRY (STN) WPI / L (QUESTEL)

Claims (2)

(57) [Claims] (A) The following formula (I): Wherein R ¹ and R ² independently of one another are hydrogen, halogen, C ₁ -C ₈ -alkyl, C ₅ -C ₆ -cycloalkyl, C ₆ -C ₁₀ -aryl, and C ₇ -C ₁₂ -aralkyl Wherein m is an integer from 4 to 7 and R ³ and R ⁴ are independently selected for each X, provided that at least one atom X both R ³ and R ⁴ represent alkyl at the same time X represents a hydrogen atom or a C ₁ -C ₆ -alkyl independently of _{one another} , X represents a hydrocarbon, and a diphenol-based thermoplastic aromatic polycarbonate corresponding to and (b) an elastomer or a component ( Mixtures containing thermoplastics other than a) and, optionally, (c) standard additives. 2. The thermoplastic aromatic polycarbonate (a) is melted, and a thermoplastic plastic (b) other than the elastomer or the component (a) and a standard additive (c) are added. 2. The method for producing a mixture according to the above item 1, wherein the mixture is homogenized in a melt.